Influence of a Pendant Amine in the Second Coordination Sphere on Proton Transfer at a Dissymmetrically Disubstituted Diiron System Related to the [2Fe]H Subsite of [FeFe]H2ase

Studies of the protonation of [Fe2(CO)4(κ2-PNP)(μ-pdt)] (1; PNP = (Ph2PCH2)2NCH3) by HBF4·Et2O showed that the nature of the reaction product depends on whether the reaction is conducted in acetone or in dichloromethane. In acetone, an N-protonated form, 2, is isolated. Tautomerization of 2 in CH2Cl2 gives rise to a μ-hydride species 3. Variable-temperature NMR experiments have been performed to clarify the processes involved.